Heterogeneous catalyst for transesterification and method of preparing same

ABSTRACT

A transesterification catalyst that is heterogeneous and a method for preparing said transesterification catalyst are provided. The catalyst can be used in a variety of transesterification reactor configurations including CSTR (continuous stirred tank reactors), ebullated (or ebullating) beds or any other fluidized bed reactors, and PFR (plug flow, fixed bed reactors). The catalyst can be used for manufacturing commercial grade biodiesel, biolubricants and glycerin.

RELATED APPLICATIONS

This application claims the benefit, and priority benefit, of U.S.Provisional Patent Application Ser. No. 62/149,138, filed Apr. 17, 2015;U.S. Provisional Patent Application Ser. No. 62/155,970, filed May 1,2015 and U.S. Provisional Patent Application Ser. No. 62/320,104, filedApr. 8, 2016 the contents of each of which are incorporated by referenceherein in their entirety.

BACKGROUND

1. Field of the Invention

The presently disclosed subject matter relates to a heterogeneouscatalyst and use of the heterogeneous catalyst for transesterification.

2. Description of the Related Art

Transesterification is the reversible chemical reaction process ofexchanging the organic group of an ester with the organic group of analcohol. Transesterification processes became commercially popular inthe 1940s as researchers explored ways to more readily produce glycerol(also called glycerin, glycerine and propanetriol) used in explosivesmanufacture during World War II. Currently, transesterification is animportant step in industrial processes such as production of: acrylatesfrom methymethacrylate, polyethylene terephthalate (PET) polymermanufacturing from ethylene glycol and either dimethyl terephthalate orterephthalic acid, and alkyl esters. Of particular current commercialinterest is the transesterification of alcohol with triglyceride esterscontained in oils and fats (primarily vegetable oils and animal fats) toform fatty acid alkyl esters and glycerin. These esters find commercialuse as biodiesel fuel and biolubricants.

Catalysts known to facilitate the transesterification reaction includemineral acids and bases, metal alkoxides, non-ionic bases and lipaseenzymes. These catalysts include homogeneous species which are solublein reactants and/or products and heterogeneous species which are solidsand insoluble in reactants or products.

Alkaline metal alkoxides (e.g., CH₃ONa for methanolysis) and alkalinemetal hydroxides (NaOH and KOH) are catalysts for the homogeneoustransesterification reaction. These catalysts are soluble in reactantsand products and thus require extensive post-reaction treatmentincluding product neutralization, salt removal and water wash to producecommercially acceptable products. These are nontrivial processes andcostly to install, maintain and operate. Homogeneous enzymatictransesterification using lipase has been utilized for conversion oftriglycerides to biodiesel, since the byproduct glycerin can be purifiedby flashing off the excess alcohol from the products. However,processing time can be lengthy for acceptable conversion oftriglycerides and product clean-up costs are high to make commercialgrade products.

Replacement of the homogeneous catalyst with heterogeneous catalyst hasbeen commercialized notably with the Esterfip-H® process licensed byAxens and the ENSEL® process licensed by Benefuel. These heterogeneouscatalyst processes can reduce post-reaction processing, but requirereaction operating temperatures of 150 degrees C. to 250 degrees C. andalcohol partial pressure as high as 300 to 400 psi for the manufactureof biodiesel alkyl esters. These heterogeneous catalyst reactions mustbe carried out in fixed bed reactors due to the severity of the processconditions.

Improvements in this field of technology are desired to reduce theoperating severity and costs of the transesterification reaction regimeas well as the subsequent process clean-up and product purificationsteps. Improvements are also desired which allow use of new technologyin existing or readily modified commercial facilities.

SUMMARY

According to the various illustrative embodiments provided herein, thepresently disclosed transesterification catalyst is a solid,heterogeneous compound having the general formula ZxQy(PO₄)nH₂O, where Zis selected from Group 1 metals including potassium, sodium and lithium,Q is selected from Group 2 metals including calcium, magnesium andbarium, x is a rational number in the range from 0.5 to 4, y is arational integer in the range from 2 to 8, and n is a rational integerin the range from 4 to 8, M can be any ceramic substrate such as, forexample, zirconia, alumina, or combinations thereof on which thecatalyst is supported. The Group 1 and Group 2 alkali metals form adouble metal salt catalyst, the phosphate (PO₄)_(n), makes it insolubleand the ceramic provides the solid support, in certain illustrativeembodiments.

In certain illustrative embodiments, the presently disclosedtransesterification catalysts can be used in a variety oftransesterification reactor configurations including CSTR (continuousstirred tank reactors), ebullated (or ebullating) beds or any otherfluidized bed reactors, and PFR (plug flow, fixed bed reactors). Thepresently disclosed transesterification catalysts can be used formanufacturing commercial grade biodiesel, biolubricants and glycerin.

In certain illustrative embodiments, a compound is provided. Thecompound can have the formula ZxQy(PO₄)nH₂O, wherein Z is selected fromthe group consisting of potassium, sodium and lithium, Q is selectedfrom the group consisting of calcium, magnesium and barium, x is arational number in the range from 0.5 to 4, y is a rational integer inthe range from 2 to 8, n is a rational integer in the range from 4 to 8,and M is a ceramic substrate on which the catalyst is supported, andwherein the compound is a transesterification catalyst. The totalsurface area of the compound can be greater than 20 square meters pergram. The active surface area of the compound can be greater than 20square meters per gram. The average diameter of the pores in thecompound can be in the range from 1-10 nanometers, The compound can beactive at a temperature in the range from 40 to 70 degrees C. Thecompound can also be active at a temperature in the range from 40 to 130degrees C.

In certain illustrative embodiments, a method of preparing atransesterification catalyst is provided. A metal hydro xide with themetal selected from the group consisting of potassium, sodium andlithium can be mixed with a metal hydroxide with the metal selected fromthe group consisting of calcium, magnesium and barium. The componentscan be mixed in a ratio of approximately 1:10 by weight to form acomponent mixture, in certain illustrative embodiments. The componentmixture can be dissolved in phosphoric acid and heated to a temperaturein the range from 60-90 degrees C. A solid compound can be precipitatedand washed. The precipitate can be mixed with ceramic substrate powderin a ratio of approximately 2:10 by weight and washed with water. Theprecipitate/ceramic substrate mixture can be calcined. Calcination canoccur at a temperature in the range from 400-500 degrees C. for 4 hoursor greater.

In certain illustrative embodiments, a method of preparing an alkylester using a transesterification catalyst is provided. The alkyl estercan be suitable for use as biodiesel fuel, as a biodiesel additive toconventional diesel fuel, or as a biolubricant additive to conventionallubricants. The alkyl ester can also be suitable for use as abiolubricant. A transesterification catalyst can be provided. Thecatalyst can have the formula ZxQy(PO₄)nH₂O, wherein Z is selected fromthe group consisting of potassium, sodium and lithium, Q is selectedfrom the group consisting of calcium, magnesium and barium, x is arational number in the range from 0.5 to 4, y is a rational integer inthe range from 2 to 8, n is a rational integer in the range from 4 to 8,and M is a ceramic substrate on which the catalyst is supported.Triglycerides and alcohol can be reacted in the presence of saidcatalyst to convert the triglycerides and alcohol to alkyl ester andglycerin. The triglycerides can be triglyceride-containing fats and/oroils. The conversion can be essentially complete conversion oftriglycerides. The glycerin can be separated from the reaction mixture.The reaction mixture can be filtered to recover the catalyst. Theunreacted alcohol can be distilled from the alkyl ester and theglycerin. The method can be at least partially performed in a continuousstirred tank reactor. The method can also be at least partiallyperformed in a fixed bed reactor. The method can also be at leastpartially performed in a fluidized bed reactor. The alkyl ester iscapable of being used as biodiesel fuel, a biodiesel additive toconventional diesel fuel, a biolubricant additive to other lubricants oras a biolubricant.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B show an illustrative embodiment of a transesterificationreaction.

FIG. 2 is a line graph comparing reaction conversion at differentmethanol molar ratios at 1 weight % of the presently disclosedtransesterification catalysts in an illustrative embodiment.

FIG. 3 is a line graph comparing reaction conversion at differenttemperatures at 1 weight % of the presently disclosedtransesterification catalysts in an illustrative embodiment.

FIG. 4 is a line graph comparing reaction conversion at differentweights of the presently disclosed transesterification catalysts at afixed temperature of 60 degrees C. in an illustrative embodiment.

FIG. 5 is a line graph comparing biodiesel (i.e., alkyl ester) yieldusing the same presently disclosed transesterification catalysts forrepeat trials in an illustrative embodiment.

While certain preferred illustrative embodiments will be describedherein, it will be understood that this description is not intended tolimit the subject matter to those embodiments. On the contrary, it isintended to cover all alternatives, modifications, and equivalents, asmay be included within the spirit and scope of the subject matter asdefined by the appended claims.

DETAILED DESCRIPTION

For the purposes of this disclosure, the transesterification catalystsof the various illustrative embodiments will hereinafter be referred toas UMAKAT. Various means for transesterification using UMAKAT are alsoprovided. According to the various illustrative embodiments providedherein, UMAKAT is a porous, solid, heterogeneous compound having thegeneral formula Z_(x)Q_(y)PO_(n)MH₂0, where Z is selected from Group 1metals including potassium, sodium and lithium, Q is selected from Group2 metals including calcium, magnesium and barium, x is a rational numberin the range from 0.5 to 4, y is a rational integer in the range from 2to 8, and n is a rational integer in the range from 4 to 8. M can be anyceramic substrate such as, for example, zirconia, silica, alumina, orcombinations thereof. The Group 1 and Group 2 alkali metals form adouble metal salt catalyst, the phosphate (PO_(n)) makes it insolubleand the ceramic provides the solid support, in certain illustrativeembodiments. UMAKAT's porous structure includes nanometer-sized poreswhich result in the material having substantial surface area.

The generic process for the transesterification reaction is shown inFIGS. 1A and 1B. FIG. 1A represents the overall transesterificationreaction, while FIG. 1B represents not only the overall reaction butalso the stepwise chemical reactions where the triglyceride (TG) esteris first converted to alkyl ester and diglyceride (DG) ester, then theDG ester is converted to alkyl ester and monoglyceride (MG) ester, andthen the MG ester is converted to alkyl ester and glycerin.

In certain illustrative embodiments, the presently disclosedtransesterification catalysts can have a total surface area greater than20 m2/gm and an active surface area greater than 20 m2/gm. As usedherein, the term “total surface area” means surface area totallyavailable, and the term “active surface area” means surface areaavailable for reaction. The active surface area of the presentlydisclosed transesterification catalysts is significant because thehigher the active surface area, the greater the availability of activecatalyst sites.

In certain illustrative embodiments, the heterogeneous compound can beporous. For example, the presently disclosed transesterificationcatalysts can have an average pore diameter in the range from 1-10nanometers (Nm). Pore diameter is measured by nitrogen adsorption. Thepore diameter of the presently disclosed transesterification catalystsis sufficient to allow migration or diffusion of reactant molecules intoand out of the pores of the presently disclosed transesterificationcatalysts, in certain illustrative embodiments. This will determine therate and extent of absorption of reactant molecules at the catalystsurfaces.

Other homogeneous transesterification processes call for the catalystbeing dissolved in an alcohol, for example, methanol or ethanol, whichneeds to be removed post reaction. Further, the homogeneous catalyst issoluble in reactants and products, which requires steps to cleanse thealkyl ester and glycerin products. In contrast, in certain illustrativeembodiments the presently disclosed transesterification catalysts canform a slurry with triglyceride-containing oils and/or fats rather thanalcohol for a better reaction conversion and easier separation ofreactants and catalyst at the end of the reaction. In general, acatalyst slurry can be made with any oil/fat rather thanmethanol/ethanol solution (or any other alcohol) for CSTR typereactions. Further, in certain illustrative embodiments the presentlydisclosed transesterification catalyst provides a uniform suspensionthroughout the reaction media. By comparison, a heterogeneous catalystsuspension in methanol/ethanol is not uniform and the catalyst particlessettle at the bottom of the reactor vessel.

In certain illustrative embodiments, the presently disclosedtransesterification catalysts can be active at significantly less severeconditions than other heterogeneous catalyst systems. For example, othermethanolysis transesterification heterogeneous catalysts requiretemperatures from 150 to 250 degrees C. and pressures of 300to 400 psi.These operating conditions require that other processes usingheterogeneous catalysts are carried out in fixed bed reactors.

In contrast, methanolysis transesterification using the presentlydisclosed transesterification catalysts to manufacture biodieselrequires temperatures in the range from 40 to 70 degrees C. andatmospheric pressure conditions, in certain illustrative embodiments.Similarly, transesterification using the presently disclosedtransesterification catalysts to react, for example, dodecanol or otherhigher alcohols and triglycerides to manufacture biolubricants requirestemperatures up to and slightly above 100degrees C. and atmosphericpressure conditions, in certain illustrative embodiments. For theseservices, the presently disclosed transesterification catalysts can beused in CSTR, fluidized bed and PFR reactor systems.

To ensure complete conversion of triglycerides, alcohol is added inexcess of stoichiometric requirements, for instance 2 to 4 times thatrequired to ensure the complete conversion of triglycerides to alkylester, in certain illustrative embodiments.

Furthermore, the presently disclosed transesterification catalyst is anefficient catalyst in that it can be reusable. The presently disclosedtransesterification catalysts can also be used in existingtransesterification process equipment without major revamping.

The presently disclosed transesterification catalysts can be used formanufacturing ASTM D 6751 biodiesel and Technical Grade glycerin as wellas biolubricants. Also, the presently disclosed transesterificationcatalysts do not need water wash for post reaction treatment and doesnot require steps such as pH neutralization to cleanse products.

In order to facilitate a better understanding of the presently disclosedsubject matter, the following examples of certain aspects of certainembodiments are given. In no way should the following examples be readto limit, or define, the scope of the presently disclosed subjectmatter.

EXAMPLE 1

UMAKAT preparation is illustrated as a double metal salt catalyst withceramic base support of zirconium oxide. In a typical catalystpreparation, 3 moles of Group 1 metal hydroxide, in this Examplepotassium hydroxide, is mixed with 1 mole of a Group 2 metal hydroxide,in this Example calcium hydroxide, and dissolved in dilute phosphoricacid. The reaction of the metal hydroxides and the acid produces adouble metal salt. This is then heated in a temperature range from 60 to90 degrees C. As a result, a white precipitate is formed which is thenwashed with water and mixed with 4 moles of zirconium oxide powder. Thismaterial is calcined at 400-500 degrees C. for a minimum of 4 hours. Theresulting material is porous, solid and heterogeneous withnanometer-sized pores with a structure that has significant surfacearea.

EXAMPLE 2

This example describes the preparation of fatty acid methyl esters bytransesterification of soybean oil with methanol using the presentlydisclosed transesterification catalysts. In a typical reaction,commercial soybean oil (100gms) and methanol (oil to methanol molarweight ratio of 1:6) and the presently disclosed transesterificationcatalysts (2 to 6 wt % of the presently disclosed transesterificationcatalysts in oil) were charged to a 500 ml glass beaker and stirred at aspeed of 300 to 500 rpm at a temperature of 60-80 degrees C. for about10 to 30 minutes. It was then allowed to cool.

The the presently disclosed transesterification catalyst was separatedby filtration from the mixture of reaction products. The product mixtureincluded unreacted methanol plus an upper layer of methyl ester and alower layer of glycerin. Then, unreacted methanol was separated fromeach layer by distillation. The methyl ester was tested in a gaschromatograph.

The methyl ester analysis report is summarized in Table 1 below alongwith the ASTM spec for biodiesel.

TABLE 1 UMAKAT ASTM SPEC Water & Sediment 0.000 .05 max Cetane Number47.8 47 min Cold Soak Filtration 90 seconds for 300 ml 300 sec max Freeglycerin 0.005% .02 max Total glycerin 0.191% .24 max Calcium, ppm <1 —Magnesium, ppm <1 — Sodium, ppm <1 — Potassium, ppm <2 —

Table 1 generally shows: no water and sediments are present in the alkylester product, only trace amounts of metals solids are present, and, asmeasured by the amount of glycerin in the product, the reaction isessentially complete conversion to methyl ester. The biodiesel made withthe presently disclosed transesterification catalysts was also assessedvia the Cold Soak Filtration Test. In this test, a biodiesel liquidsample is chilled to below 32 degrees F. for 16 hours, restored to roomtemperature and passed thru a 0.5 micron filter. This ASTM test ispassed if the filtration is complete within 300 seconds. The biodieselof the presently disclosed transesterification catalysts passed thru thefilter in 90 seconds.

Different oils and fats were tested for oil conversion to methyl esterusing UMAKAT and the results are tabulated in the following table:

TABLE 2 Test % Oil No. Oil/Fat Alcohol conversion Notes 2 Canola OilMethanol 97.7 — 3 Yellow grease Methanol 96.8 — 4 Coconut Oil Methanol98.2 — 5 Cottonseed Oil Methanol 97.5 — 6 Chicken Fat Methanol 97.2 HighFree Fatty Acid (“FFA”) Oil first esterified with acid catalyst

Table 2 shows that the presently disclosed transesterification catalystis effective for a wide variety of oils and fats.

FIGS. 2 thru 5 are heterogeneous catalytic kinetics graphs showing howthe reaction proceeds at different temperatures, methanol ratios, andcatalyst weight concentrations.

In certain illustrative embodiments, the presently disclosedtransesterification catalysts can be easily separated from reactants andproducts and reused, no leaching of metal ions into the reactant mixturewas observed, and processing temperature and pressure of the presentlydisclosed transesterification catalysts are at moderate conditions whichare significantly less severe than other heterogeneous catalytictransesterification processes.

Additionally, in certain illustrative embodiments the presentlydisclosed transesterification catalysts can be used to process lowcost/unrefined oils and/or fats containing impurities that, for example,cause discoloration of the feedstock. Further, post reaction processwaste is reduced as neutralization and water wash of products are notrequired. Relative to other catalysts and processes, the presentlydisclosed transesterification catalyst is highly active at comparativelylow temperature and pressure. Also, the presently disclosedtransesterification catalyst produces much fewer impurities in the alkylester and glycerin products and thus the products are much cleaner atthe end of the reaction. Further, no pH neutralization water wash isrequired and salts from glycerin neutralization do not end up in thealcohol distillation column. Finally, transesterification facilities ofthe presently disclosed transesterification catalysts are comparativelylower in cost to install, maintain and operate.

As used herein, the term “in the range from” and like terms is inclusiveof the values at the high and low end of said ranges, as well asreasonable equivalents.

While the disclosed subject matter has been described in detail inconnection with a number of embodiments, it is not limited to suchdisclosed embodiments. Rather, the disclosed subject matter can bemodified to incorporate any number of variations, alterations,substitutions or equivalent arrangements not heretofore described, butwhich are commensurate with the scope of the disclosed subject matter.

Additionally, while various embodiments of the disclosed subject matterhave been described, it is to be understood that aspects of thedisclosed subject matter may include only some of the describedembodiments. Accordingly, the disclosed subject matter is not to be seenas limited by the foregoing description, but is only limited by thescope of the appended claims.

What is claimed is:
 1. A method of preparing alkyl ester using atransesterification catalyst, the method comprising: providing atransesterification catalyst having the formula Z_(x)Q_(y)(PO₄)_(n)H₂O,wherein: Z is selected from the group consisting of sodium and lithium,Q is selected from the group consisting of calcium and barium, x is arational number in the range from 0.5 to 4, y is a rational integer inthe range from 2 to 8, and n is a rational integer in the range from 4to 8; and wherein the transesterification catalyst having the formulaZ_(x)Q_(y)(PO₄)_(n)H₂O is supported on a ceramic substrate; and reactingone or more triglycerides and an alcohol in the presence of the catalystand converting the triglycerides and alcohol to alkyl ester andglycerin.
 2. The method of claim 1, wherein the triglycerides comprisetriglyceride-containing fats and/or oils.
 3. The method of claim 1,wherein the converting of triglycerides comprises producing essentiallycomplete conversion of the triglycerides to alkyl ester and glycerin. 4.The method of claim 1, further comprising: separating the glycerin fromthe alkyl ester and catalyst; filtering the alkyl ester to recover thecatalyst; and distilling the unreacted alcohol from the alkyl ester andthe glycerin.
 5. The method of claim 1, wherein the method is at leastpartially performed in a continuous stirred tank reactor.
 6. The methodof claim 1, wherein the method is at least partially performed in afixed bed reactor.
 7. The method of claim 1, wherein the method is atleast partially performed in a fluidized bed reactor.
 8. The method ofclaim 1, wherein the alkyl ester is capable of being used as biodieselfuel.
 9. The method of claim 1, wherein the alkyl ester is capable ofbeing used as biodiesel additive to conventional diesel fuel.
 10. Themethod of claim 1, wherein the alkyl ester is capable of being used as abiolubricant additive to other lubricants.
 11. The method of claim 1,wherein the alkyl ester is capable of being used as a biolubricant.